CN106397112A - Preparation method for continuous production of 1,2-pentanediol - Google Patents
Preparation method for continuous production of 1,2-pentanediol Download PDFInfo
- Publication number
- CN106397112A CN106397112A CN201610701561.3A CN201610701561A CN106397112A CN 106397112 A CN106397112 A CN 106397112A CN 201610701561 A CN201610701561 A CN 201610701561A CN 106397112 A CN106397112 A CN 106397112A
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- Prior art keywords
- pentanediol
- formic acid
- method producing
- continuous preparation
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
- C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a preparation method for continuous production of 1,2-pentanediol, main technical points are as follows: using a tubular reactor, using 1-pentene as a raw material and using a peroxide as an oxidant for epoxidation in a system with an organic acid as a solvent, adding an alkali for neutralization to remove the organic acid, after the reaction is completed, adjusting to be neutral, extracting, drying and rectifying to obtain the 1,2-pentanediol with the purity of more than 99.0%. The reaction time is shortened to 2h, the reaction yield is more than 82%, continuous industrial production can be realized, the yield is improved, reaction equipment floor space is small, cost is saved, three-waste emissions can be reduced, postprocessing operation is simple, environmental pollution is less, reaction operation safety is high, and industrialization is facilitated.
Description
Technical field
The invention belongs to the synthetically prepared field of chemical products is and in particular to one kind continuously produces the preparation of 1,2- pentanediol
Method.
Background technology
1,2- pentanediol is a kind of colourless transparent liquid, is dissolved in the organic solvents such as alcohol, ether and ethyl acetate.1,2- pentanediol
Be widely used in the whole world, in addition to as bactericide propiconazole key intermediate and cosmetic formulations, be also produce polyester fiber,
The important source material of the products such as surfactant, medicine；1,2- pentanediol is the glycol of straight chain, has obvious polarity and non-pole
Property, so that it has the property differing from other glycol, this special distribution of charges explains its exclusive characteristic and many
Feature.Can be mixed with multiple compounds with multiple ratios, non-corrosiveness, there is the active component of dissolving indissoluble, for skin care
In the various skin-protection product such as frost, eye cream, surfactant, infant care product, sunscreen product.Structural formula is as follows：
1,2- pentanediol domestic before manufacturing enterprise less, particularly the larger enterprise of yield does not almost have, this make domestic must
Palpus dependence on import, to meet demand, largely constrains the development of China's propiconazole.Main cause is PETROLEUM PROCESSING industry
C5Cut uses generally as fuel, and separating through rectifying can be used as the amylene of raw material or its deep processing product 1,2- epoxy penta
Alkane does not almost have.The synthesis technique of existing document report mainly has two kinds：One kind is positive valeric acid method：With positive valeric acid as raw material, warp
Cross bromo, hydrolysis and reduction reaction and obtain 1,2- pentanediol.This method will to the consersion unit of bromo-reaction and production process
Ask condition harsh, produce substantial amounts of waste water, waste gas is difficult to process, high cost, environmental pollution is serious, consuming man-hour is many, post processing
Complex operation is it is difficult to form large-scale production；Another kind is n-amyl alcohol method, with n-amyl alcohol as raw material, through hydrolysis, oxidation, water
Solution, neutralization obtain 1,2- pentanediol.This method can not continuously produce, and belongs to step, and area of mill site is big, artificial one-tenth
This height, yield are little, reaction efficiency is low it is impossible to mass produce.In addition, some document reports are selected in sodium hydroxide hydrolysis and system
Standby 1,2- pentanediol, but there is substantial amounts of salt to produce when the method finally concentrates, lead to yield low, NaOH alkalescence itself is too
By force, release substantial amounts of heat in reaction, in production, have larger potential safety hazard.
These are unfavorable for industrialization large-scale production and improve product quality, need exploitation a kind of stable, efficient, safe,
Low cost, post-processing operation is simple, and environmental pollution is little, and operation is safe, and reaction yield is high, and good product quality is beneficial to
Industrialized 1, the preparation method of 2 pentanediols.
Content of the invention
It is an object of the invention to provide a kind of continuous preparation method producing 1,2- pentanediol.
Based on above-mentioned purpose, this invention takes following technical scheme：
A kind of continuous preparation method producing 1,2- pentanediol, with amylene as raw material,（Commercially available）With peroxide as oxidant, first
Acid is for, under the system of solvent, through peroxidization, removing organic acid, plus alkali neutralization, then acid adding is counter is adjusted to neutrality, washing, extraction,
1, the 2- pentanediol that purity is more than 99% is can get after rectifying.
The above-mentioned a kind of continuous preparation method producing 1,2- pentanediol, using gas-liquid tubular reactor.Duct type reacts
Device is laminated by polylith sheet frame, and there is the very how tiny groove not advising side on each sheet frame two sides, and two sheet frame faces are combined
Form numerous micro-tubes.There is interlayer inside sheet frame, connect heating, cooling system, for adjusting reaction temperature.
Above-mentioned oxidizing reaction temperature is 20 DEG C～30 DEG C, insulation reaction 2 hours, and sampling TLC monitors complete to raw material reaction
Entirely；
Sodium carbonate neutralization is added, temperature control is at 40 DEG C～50 DEG C in above-mentioned post processing reaction；
Above-mentioned extraction organic solvent is methyl tertiary butyl ether(MTBE), ethyl acetate.
The present invention uses advanced pipeline reactor to substitute original reaction tank reactor, and technique effect shows as：
1st, the reaction time greatly shortens, and reaction rate improves, because the cross section of pipeline reactor is little, gas passes through cross section
When contact limited, the possibility completely attaching to material increases；The single height of pipeline reactor exceeds well over the effective of reactor
Highly, the time growth multiplying power of contacting material is the same as height multiplying power；
2nd, investment is saved：Because device structure is relatively easy, the device of equal production capacity will be still reaction 1/4-1/3,
Saves significantly on equipment investment, and operating flexibility ratio is larger, can accomplish that 0.3-1.2 multiplying power produces.
3rd, pipeline reactor temperature control is simple, easy control of temperature, and operation is safe, installs simple, operation reliability,
Safety.
4th, save energy consumption：Eliminate the high-power electric consumption such as large-scale stirring.Reaction rate accelerates also necessarily to reduce heat energy
The amount consuming.
5th, artificial saving：Oxidation only needs to people's supervision, produces the manpower reducing 1/2 compared with equal stills for air blowing.
Specific embodiment
Below by way of specific embodiment, technical scheme is described in further detail, but the protection model of the present invention
Enclose and be not limited thereto.
Embodiment 1
A kind of continuous method producing 1,2 pentanediols
Comprise the following steps that：
Pipeline reactor is provided with two charging apertures, charging aperture 1, charging aperture 2, and connecting charging aperture 1 has 1 pipeline carrying stirring
Reactor；Formic acid（Commercially available）870kg, hydrogen peroxide（50）650kg is passed through pipeline by charging aperture 1 after being uniformly mixed, charging
Mouth 2 is passed through 1- amylene 470kg, is heated to 20 DEG C～30 DEG C, insulation reaction 2 hours, sampling sampling TLC（Solvent is acetic acid second
Ester：Ethanol=4：1）Detection, to n-pentene reaction completely, releases material by outlet and is post-processed in reactor, keep
Add raw material from charging aperture；During post processing, need to be warming up to when 40 DEG C～50 DEG C and add sodium carbonate neutralization, then be adjusted with technical hydrochloric acid
PH=7, near room temperature, add 800kg methyl tertiary butyl ether(MTBE), stir 30 minutes, then stratification, upper strata is organic layer（Produce
Product）, lower floor is that water layer, water layer are extracted with methyl tertiary butyl ether(MTBE) again, merges organic layer, organic layer anhydrous magnesium sulfate is dried, steams
Evaporate rectifying after recycling design, collect the just boiling for 120 DEG C～125 DEG C/650KPa for the top temperature, obtain 291.5kg 1,2- pentanediol,
Product purity is 99.8%, and yield is 83.5% (in terms of n-pentene).
Embodiment 2
A kind of method of continuous production 1,2- pentanediol
Comprise the following steps that：
Pipeline reactor is provided with two charging apertures, charging aperture 1, charging aperture 2, and connecting charging aperture 1 has 1 pipeline carrying stirring
Reactor；Formic acid（Commercially available）870kg, hydrogen peroxide（50）650kg is passed through pipeline by charging aperture 1 after being uniformly mixed, charging
Mouth 2 is passed through n-pentene 470kg, is heated to 20 DEG C～30 DEG C, insulation reaction 2 hours, sampling sampling TLC（Solvent is acetic acid second
Ester：Ethanol=4：1）Detection, to n-pentene reaction completely, releases material by outlet and is post-processed in reactor, keep
Add raw material from charging aperture；During post processing, need to be warming up to when 40 DEG C～50 DEG C and add sodium carbonate neutralization, then be adjusted with technical hydrochloric acid
PH=7, near room temperature, add 800kg ethyl acetate, stir 30 minutes, then stratification, upper strata is organic layer（Product）, under
Layer is water layer, water layer is extracted with ethyl acetate again, merges organic layer, organic layer anhydrous sodium sulfate drying, distillating recovering solvent
Rectifying afterwards, collects the just boiling for 120 DEG C～125 DEG C/650KPa for the top temperature, obtains 1, the 2- pentanediol of 283.6kg, product purity is
99.5%, yield is 82.0% (in terms of n-pentene).
Claims (7)
1. a kind of continuous preparation method producing 1,2- pentanediol, it is characterised in that utilizing pipeline reactor, is former with amylene
Material, with peroxide as oxidant, under the system for solvent for the organic acid, through peroxidization, removing organic acid, adds in alkali
With then acid adding is counter is adjusted to neutrality, extraction, washing, is dried, and can get 1, the 2- pentanediol that purity is more than 99.0%, instead after rectifying
Answer formula as follows：
.
2. a kind of continuous preparation method producing 1,2- pentanediol according to claim 1 is it is characterised in that use is anti-
Answer device to be Air-liquid pipeline formula reactor, have charging aperture and discharging opening, continuous feed and discharging.
3. a kind of continuous preparation method producing 1,2- pentanediol according to claim 1 it is characterised in that with 1- amylene,
Formic acid, hydrogen peroxide are raw material, and with formic acid as catalysts and solvents, hydrogen peroxide and Oxidation of Formic Acid react generation performic acid, mistake
Formic acid and 1- amylene oxidation reaction in formic acid system generates 1,2- epoxypentane.
4. a kind of continuous preparation method producing 1,2- pentanediol according to claim 1, formic acid and hydrogen peroxide mole
Ratio is 1: 0.98；The mol ratio of 1- amylene and formic acid is 1: 2.8.
5. a kind of continuous preparation method producing 1,2- pentanediol according to claim 1 is it is characterised in that oxidizing temperature
Control at 20 DEG C～30 DEG C.
6. a kind of continuous preparation method producing 1,2- pentanediol according to claim 1 is it is characterised in that add sodium carbonate
Neutralization open loop, Open loop temperature controls at 40 DEG C～50 DEG C.
7. a kind of continuous preparation method producing 1,2- pentanediol according to claim 1, post-processing operation is, with industry
Salt acid for adjusting pH is to neutral, extraction, dry, rectifying；Extractant methyl tertiary butyl ether(MTBE) or ethyl acetate；Drier is anhydrous sulphur
Sour magnesium or anhydrous sodium sulfate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610701561.3A CN106397112A (en) | 2016-08-23 | 2016-08-23 | Preparation method for continuous production of 1,2-pentanediol |
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| CN201610701561.3A CN106397112A (en) | 2016-08-23 | 2016-08-23 | Preparation method for continuous production of 1,2-pentanediol |
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| CN201610701561.3A Pending CN106397112A (en) | 2016-08-23 | 2016-08-23 | Preparation method for continuous production of 1,2-pentanediol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283046A (en) * | 2019-07-31 | 2019-09-27 | 新乡市巨晶化工有限责任公司 | A kind of preparation method of 1,2- pentanediol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479021A (en) * | 1983-08-30 | 1984-10-23 | Ciba-Geigy Corporation | Continuous process for producing 1,2-alkanediols |
| US4605795A (en) * | 1984-11-24 | 1986-08-12 | Degussa Aktiengesellschaft | Continuous process for the production of pentanediol-1,2 |
| CN1552684A (en) * | 2003-05-29 | 2004-12-08 | 浙江联盛化学工业有限公司 | Preparing method for 1,2-pentadiol |
| CN101967082A (en) * | 2010-04-12 | 2011-02-09 | 宁波中化化学品有限公司 | Method for preparing 1,2-pentadiol |
| CN104926600A (en) * | 2015-05-12 | 2015-09-23 | 佛山市德品高新材料有限公司 | Method for synthesizing 1,2-pentanediol by one-pot method |
-
2016
- 2016-08-23 CN CN201610701561.3A patent/CN106397112A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479021A (en) * | 1983-08-30 | 1984-10-23 | Ciba-Geigy Corporation | Continuous process for producing 1,2-alkanediols |
| EP0141775A1 (en) * | 1983-08-30 | 1985-05-15 | Ciba-Geigy Ag | Continuous process for the production of 1,2-alkane diols |
| US4605795A (en) * | 1984-11-24 | 1986-08-12 | Degussa Aktiengesellschaft | Continuous process for the production of pentanediol-1,2 |
| CN1552684A (en) * | 2003-05-29 | 2004-12-08 | 浙江联盛化学工业有限公司 | Preparing method for 1,2-pentadiol |
| CN101967082A (en) * | 2010-04-12 | 2011-02-09 | 宁波中化化学品有限公司 | Method for preparing 1,2-pentadiol |
| CN104926600A (en) * | 2015-05-12 | 2015-09-23 | 佛山市德品高新材料有限公司 | Method for synthesizing 1,2-pentanediol by one-pot method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283046A (en) * | 2019-07-31 | 2019-09-27 | 新乡市巨晶化工有限责任公司 | A kind of preparation method of 1,2- pentanediol |
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Application publication date: 20170215 |